1

The environmentally benign pulping process of non-wood fibers.

Waranyou Sridach

3Department of Material Product Technology, Faculty of Agro-Industry, Prince of

4Songkla University.
5
6

Abstract

7
8The increasing demand for paper has raised the need for low-cost raw materials and
9also the developing of new process in order to boost production. Non-wood fibers, for
10example agricultural residues and annual plants, are considered an effective
11alternative source of cellulose for producing pulp and paper sheets with acceptable
12properties. This paper reviews some physical and chemical properties of non-wood
13pulps which have effects on the making of paper. The less polluting pulping processes
14that use organic solvents are of interest for pulp production. The delignification of the
15organosolv pulping process depends on the type of organosolv methods and cellulosic
16sources used. The chemicals and cooking conditions, such as the catalysts, solvent
17concentration, cooking temperature, cooking time, and liquor to raw material ratio, all
18influence the properties of the pulp and paper.
19
20Keywords : Non-wood fiber, Organosolv, Alcohol pulping, Solvent-based pulping,
21Delignification

1Introduction
2Pulp and paper production is one of the high demand sectors in the world of industrial
3production. The total global consumption from paper-making was projected to
4increase from 316 million tons in 1999 and 351 million tons in 2005 to about 425
5million tons by 2010 (Garca et al., 2008). Progress in pulp and paper technology has
6overcome most of the related environmental problems. The environmental problems
7have brought forth the cleaner technology now involved in paper making. New raw
8materials have replaced traditional wood raw materials with non-wood and residual
9materials, and less polluting cooking and pulp bleaching processes have been evolved.
10
11Cleaner technology is applied to achieve increased production with minimum effect
12on the environment and to save, utilize, and recycle expensive and scarce chemicals
13and raw materials. This technology is also called low and non-waste technology
14(Mller, 1986). The technology lessens the disposal costs, stability risks and resource
15costs and results in a reduced burden on the natural environment and increases profits.
16New technology is essential for a clean industry, but this option is largely suppressed
17because of the costs of the technology required. Some studies have looked specifically
18into the environmental consequences of pulp and paper production using wood as the
19feedstock (Avar and Demirer, 2008; Young and Akhtar, 1998; Environment Canada,
202003; Sadownic et al., 2005; Thompson et al., 2001).
21Non-wood fibers
22There is growing interest in the use of non-wood such as annual plants and
23agricultural residues as a raw material for pulp and paper. Non-wood raw materials
24account for less than 10% of the total pulp and paper production worldwide (El-

1Sakhawy et al., 19996). This is made up of 44% straw, 18% bagasse, 14% reeds, 13%
2bamboo and 11% others (see Figure 1). The production of non-wood pulp mainly
3takes place in countries with a shortage of wood, such as China and India (Oinonen
4and Koskivirta, 1999). China accounts for more than two thirds of the non-wood pulp
5produced worldwide (Hammett et al., 2001).
6
7The utilization of non-wood fibers is an ethically sound way to produce pulp and
8paper compared to the clear-cutting of rain forests or primeval forests. The benefits of
9non-wood plants as a fiber resource are their fast annual growth and the smaller
10amount of lignin in them that bind their fibers together. Another benefit is that non11wood pulp can be produced at low temperatures with lower chemical charges. In
12addition, smaller mill sizes can be economically viable, giving a simplified process.
13Non-wood pulps are also more easily refined. Moreover, non-food applications can
14give additional income to the farmer from food crops or cattle production (Rodrguez
15et al, 2007; Rousu et al., 2002; Kissinger et al., 2007).
16
17Non-wood fibers are used for all kinds of paper. Writing and printing grades produced
18from bleached non-wood fiber are quite common. Some non-wood fibers are also
19used for packaging. This reflects the substantially increased use of non-wood raw
20materials, from 12,000 tons in 2003 to 850,000 tons in 2006 (FAO, 2009; Lpez et al.,
212009). Given that world pulp production is unlikely to increase dramatically in near
22future, there is a practical need for non-wood pulp to supplement the use of
23conventional wood pulp (Diesen, 2000).

1According to their origin, non-wood fibers are divided into three main types: (1)
2agricultural by-products; (2) industrial crops; and (3) naturally growing plants
3(Rowell and Cook, 1998; Svenningsen et al., 1999). Agricultural by products are the
4secondary products of the principal crops (usually cereals and grains) and are
5characterized by low raw material price and moderate quality, such as rice straw and
6wheat straw (Navaee-Ardeh et al., 2003; Deniz et al., 2004). Industrial crops, such as
7hemp and kenaf, can produce high quality pulps with high expense cost of raw
8materials. However, the source of the pulp is limited and these materials come from
9crops planted specifically to yield fiber (Zomers et al., 1995; Kaldor et al., 1990).
10Naturally growing plants are also used for the production of high quality pulps. This
11includes bamboo and some grass fibers, such as elephant grass, reed and sabai grass
12(Salmela et al., 2008., Walsh, 1998, Shatalov and Pereira, 2002; Poudyal, 1999). The
13specific physical and chemical characteristics of non-wood fibers have an essential
14role in the technical aspects involved in paper production. On the other hand, the
15technical issues involved are related to the economic, environmental and ethical
16contexts and vice versa.
17Properties of non-wood fibers
18The chemical compositions of non-wood materials have tremendous variations in
19chemical and physical properties compared to wood fibers (Gmukaya and Usta,
202002; Rezayati-Charani et al., 2006). They vary, depending on the non-wood species
21and the local conditions, such as soil and climate (Bicho et al., 1999; Jacobs et al.,
221999). The non-wood materials generally have higher silicon, nutrient and
23hemicellulose contents than wood (Hurter, 1988). Some parts of the non-fibrous
24materials may be removed by the pre-treatment of the raw material, which has a
25positive influence on the ash content and the pulp and paper properties. Table 1 shows

1the average results of the chemical and physical analyses of some non-wood fibers
2(Hurter, 1988; Chen et al., 1987; Rodrguez et al., 2008). The standard deviations of
3the three replicates in each test with respect to the means were always less than 10%.
4
5Short fiber length, high content of fines and low bulk density are the most important
6physical features of non-wood raw materials (Oinonen and Koskivirta, 1999;
7Paavilainen, 2000). The large amount of fines and the short fiber length especially
8affect the drainage properties of pulp. Apart from the operation of the pulp mill itself,
9these properties also affect dewatering in the paper machine. Due to the wide range of
10different non-wood species and their different physical properties, substantial
11differences in dewatering behavior may arise. (Cheng and Paulapuro, 1996a,b). The
12low bulk density affects the logistics of non-wood raw materials. This would make
13the amount of cellulose handled comparable to wood.
14
15The production of pulp from non-wood resources has many advantages such as easy
16pulping capability, excellent fibers for the special types of paper and high-quality
17bleached pulp. They can be used as an effective substitute for the forever decreasing
18forest wood resources (El-Sakhawy et al., 1995; 1996; Jimnez et al., 2007). In
19addition to their sustainable nature, other advantages of non-wood pulps are their easy
20pulping and bleaching capabilities. These allow the production of high-quality
21bleached pulp by a less polluting process than hardwood pulps (Johnson, 1999) and
22reduced energy requirements (Rezayati-Charani et al., 2006). However, some mineral
23substances in their composition, including K, Ca, Mn, Cu, Pb and Fe, may have
24negative effects on the different steps of pulp and paper manufacturing, especially the

1bleaching process. Metals may interfere during the bleaching with hydrogen peroxide
2or ozone. The transition elements form radicals that react unselectively with the pulp
3when the pulp is bleached without chlorine chemicals (Gierer, 1997). Furthermore,
4bleaching is accompanied by the formation of oxalic acid. Calcium reacts with oxalic
5acid to form calcium oxalate, which deposits easily. Thus effluent-free bleaching will
6obviously be difficult to achieve in the bleaching plant (Dexter and Wang, 1998).
7Non-wood pulping
8Traditionally non-wood material is cooked with hybrid chemimechanical and alkali9based chemicals (Goyal et al., 1992; Jahan et al., 2007). Hybrid chemimechanical
10pulps, which were once thought of as a logical replacement for chemical pulps, simply
11do not provide the purity necessary for high grade and dissolving pulps.
12Chemimechanical pulps cannot be used in grades that do not allow fiber-containing
13furnishes due to brightness reversion, brightness levels, or simply customer insistence.
14Much more money is spent each year on environmental projects in an attempt to
15resolve some of the problems associated with the pulping process. Solving these
16motivates much the research and development in relation to new pulping
17technologies.
18
19In chemical pulping, the raw materials are cooked with appropriate chemicals in an
20aqueous solution at an elevated temperature and pressure. The objective is to degrade
21and dissolve away the lignin and leave behind most of the cellulose and
22hemicelluloses in the form of intact fibers. In practice, chemical pulping methods are
23successful in removing most of the lignin; they also degrade and dissolve a certain
24amount of the cellulose and hemicelluloses (Smook, 1994).

1Non-wood pulping processes generate large volumes of black liquor as by-products

2and wastes. Black liquor wastewater is a mixture of organic and inorganic materials,
3with very high amounts of total dissolved solids (TDS). The total dissolved solids in
4the black liquor are composed of lignin derivatives, low molecular weight organics,
5and the rest being made up of chemicals from the digesting liquor (Huang et al.,
62007). In delignification, the relatively high amount of silicon present in non-wood
7material is dissolved together with lignin into cooking liquor, This has led to
8difficulties in the recovery of cooking chemicals. This situation makes black liquor
9one of the most difficult materials to handle in wastewater treatment processes.
10
11Generally, alkaline non-wood pulps contain much hemicellulose while their fibers are
12short. This impairs the dewatering properties in different unit processes, the adhesive
13forces in the paper machine, and paper quality. Then the hemicellulose content of the
14pulp should be controlled to avoid these problems. However, when using the alkaline
15pulping processes, the hemicellulose content of the pulp cannot be easily controlled
16without losses in pulp quality (Rousu et al., 2002).
17
18The conventional alkaline pulping process is not suitable for many non-wood raw
19materials and caused serious environmental problems. Therefore, throughout the
20world many alternative pulping processes have been introduced. One group of the
21most promising alternative processes is called the Organosolv processes. These
22cooking methods are based on cooking with organic solvents such as alcohols or
23organic acids. Methanol and ethanol are common alcohols used and the organic acids
24are normally formic acid and acetic acid. High cooking temperatures and associated

1high pressures are needed when alcohols are used in cooking. However, organic acids
2require lower temperatures and the pressure is closer to atmospheric pressure. Other
3more unusual solvents include various phenols, amines, glycols, nitrobenzene,
4dioxane, dimethylsulfoxide, sulfolane, and liquid carbon dioxide (Sunquist, 2000).
5Organosolv pulping of Non-wood
6The Organosolv process has certain advantages. It makes possible the breaking up of
7the lignocellulosic biomass to obtain cellulosic fibers for pulp and papermaking, high
8quality hemicelluloses and lignin degradation products from generated black liquors,
9thus avoiding emission and effluents (Aziz and Sarkanen, 1989; Hergert, 1998;
10Paszner, 1998; Sidiras and Koukios, 2004).
11
12The Organosolv processes use either low-boiling solvents (for example methanol,
13ethanol, acetone), which can be easily recovered by distillation. It may use high14boiling solvents (for example ethyleneglycol, ethanolamine), which can be used at a
15low pressure and hence at available facilities currently used in classical pulping
16processes. Thus it is possible to use the equipment used in the classic processes, for
17example the soda and Kraft processes, thus saving capital costs. (Muurinen, 2000;
18Lpez et al., 2006; Rodrguez and Jimnez, 2008; Lavarack et al., 2005). Using this
19process, pulps with properties such as high-yield, low residual lignin content, high
20brightness and good strength can be produced (Shatalov and Pereira, 2004; Yawalata
21and Paszner, 2004). Moreover, valuable byproducts include hemicelluloses and
22sulphur-free lignin fragments. These are useful for the production of lignin-based
23adhesives and other products due to their high purity, low molecular weight, and

1easily recoverable organic reagents (Mcdonough, 1993, Dapa et al., 2002; Pan et al.,
22005).
3
4In recent years research into the Organosolv pulping processes has led to the
5development of several Organosolv methods capable of producing pulp with
6properties near those of Kraft pulp. Prominent among the processes that use alcohols
7for pulping are those of Kleinert (Aziz and Sarkanen, 1989), Alcell (Aziz and
8Sarkanen, 1989; Lnnberg et al., 1987; Stockburger, 1993), MD Organocell (Aziz and
9Sarkanen, 1989; Lnnberg et al., 1987; Stockburger, 1993), Organocell (Lnnberg et
10al., 1987; Stockburger, 1993; Dahlmann and Schroeter, 1990), ASAM (Lnnberg et
11al., 1987; Black, 1991), and ASAE (Kirci et al., 1994). Other processes based on
12other chemicals also worthy of special note are ester pulping (Aziz and McDonough,
131987; Young, 1989), phenol pulping (Aziz and Sarkanen, 1989; Funaoka and Abe,
141989), Acetocell (Neumann and Balser, 1993), Milox (Poppius-Levlin et al., 1991,
15Sundquist and Poppius-Levlin, 1992;Sundquist and Poppius-Levlin 1998), Formacell
16(Saak et al., 1995) and NAEM (Paszner and Cho, 1989).
17
18Organosolv pulping processes, by replacing much or all of the water with an organic
19solvent, delignify by chemical breakdown of the lignin prior to dissolving it. The
20cleavage of ether linkages is primarily responsible for lignin breakdown in
21Organosolv pulping. The chemical processing in Organosolv pulping is fairly well
22understood (McDonough, 1993). High cooking temperature and thus high pressures
23are needed when alcohols are used in cooking. However, organic acids require lower
24temperatures and the pressure is closer to atmospheric.

10

1The ethanol Organosolv process was originally designed to produce clean pulping and
2was further developed into the Alcell process for pulp production (Pye and Lora,
31991). The Alcell process is a solvent-pulping process that employs a mixture of
4water and ethanol (CH2H5OH) as the cooking medium. The process can be viewed as
5three separate operations: extraction of lignin to produce pulp; lignin and liquor
6recovery; and by-product recovery (Stockburger, 1993). The raw materials are cooked
7in a 50:50 mixture of water and ethanol at around 175-195C for 1hour. The typical
8liquid to biomass solid ratio is 4-7 and a liquor pH of about 2-3. The system employs
9liquor-displacement washing at the end of the cooking to separate the extracted lignin.
10The sulfur-free lignin produced with this process has very high purity and has the
11potential of high-value applications. Furthermore, this process generates the furfural
12which is used as the solvent for lubricating oil production. It is claimed that the
13process produces pulps with a higher yield that bleach more easily and are free of
14sulfur emissions. The Alcell process enjoys a significant capital cost advantage
15compared with the Kraft process, since it does not require a recovery furnace or other
16traditional chemical recovery equipment (such as lime kilns and causticizers).
17
18The methanol Organosolv process has been used in the alkaline sulphite19anthraquinone-methanol process (ASAM) and the soda pulping method with methanol
20(Organocell). The ASAM process is basically alkaline sulfite pulping with the
21addition of anthraquinone (AQ) and methanol (CH 3OH) to achieve a higher
22delignification level (Stockburger, 1993). The process has been successful in the
23pulping of softwood, hardwood and also non-wood material. The active cooking
24chemicals of the ASAM process are sodium hydroxide, sodium carbonate and sodium
25sulphite. The addition of methanol to the alkaline sulphite cooking liquor considerably

11

1improves delignification and the process produces pulp with better strength properties,
2higher yields and better bleachability compared to the Kraft process.
3
4The ASAM process utilizes sodium hydroxide, sodium carbonate, sodium sulfite
5(Na2SO3), methanol, and small amounts of the catalyst anthraquinone. ASAM cooking
6liquor normally contains about 10% methanol by volume. The anthraquinone dose is
70.05%-0.1% by weight for fibrous materials. The liquor-to-raw material ratio is 3-5:1,
8and the cooking temperature and time are 175C and 60-150 minutes, respectively.
9Anthraquinone serves as a catalyst to increase the reaction rate. Methanol is added to
10assist in dissolving the lignin and acts as a buffer, prevents lignin from condensing
11and stabilizes the carbohydrates (Muurinen, 2000). Methanol also improves the
12solubility of the anthraquinone. The strength properties of ASAM pulps have been
13found to be equivalent to Kraft pulps while at a higher yield and lower residual lignin
14content. It is more environmentally benign, since the process is free of the reduced
15sulfur compounds produced in the Kraft process. Unbleached ASAM pulps also have
16higher initial brightness and thus lend themselves well to totally chlorine-free
17bleaching sequences. Methanol improves the impregnation of the chemicals.
18
19The Organocell process is a solvent pulping process that uses sodium hydroxide,
20methanol, and catalytic amounts of anthraquinone as the pulping chemicals
21(Stockburger, 1993). The Organocell process was originally a two-stage process. The

22first stage is cooking with aqueous methanol, a 50% methanol solution, at 190 C for
2320-50 minutes. This stage operates at a mildly acidic condition due to a deacetylation
24of the raw material. The main part of the sugars and 20 % of lignin is dissolved in this

12

1stage. The second stage involves the addition of sodium hydroxide at an 18-22%

2concentration at temperatures of 160-170 C (Kinstrey, 1993).

3
4For the new Oganocell pulping process, the first stage was eliminated from the
5process. The resultant single stage process is operated with sodium hydroxide,
6methanol, and catalytic amounts of anthraquinone as cooking chemicals. The
7concentration of methanol in the cooking liquor is in the range of 25-30%. The one
8stage process is easier to control and the elimination of the first stage results in
9stronger fibers than those from the two stage process (Leponiemi, 2008). Methanol
10improves the capacity of the cooking liquor to penetrate into the fibrous materials and
11renders the lignin more soluble. Anthraquinone functions in the same way as in soda
12cooking by stabilizing polysaccharides and accelerating lignin dissolution (Sundquist,
132000). Methanol is recovered by evaporation and distillation. Lignin is precipitated in
14evaporation by decreasing the pH of the liquor and it can be separated using a
15centrifuge. Organocell pulps produced at a pilot operation are almost as good as the
16corresponding Kraft pulps in yield and physical characteristics. The organocell pulps
17were also found to bleach more easily. The process is suitable for hardwood, softwood
18and non-wood species. The process also is entirely free of the sulfur emissions found
19in the traditional Kraft and sulfite processes (Aziz and Sarkanen, 1989).
20
21Organic acid processes are alternative methods of organosol pulping to delignify
22lignocellulosic materials to produce pulp for paper (Poppius et al., 1991; Jimnez et
23al., 1998; Lam et al., 2001; Kham et al., 2005a,b). Typical organic acids used in the
24acid pulping methods are formic acid and acetic acid. The process is based on acidic

13

1delignification to remove lignin, a necessary part of the hemicellulose and nutrients,

2while silicon remains in the pulp. The pulping operation can be carried out at
3atmospheric pressure. Acid used in pulping can be easily recovered by distillation and
4re-used in the process (Muurinen, 2000). Cellulose, hemicellulose and lignin can be
5effectively separated by degradation in aqueous acetic acid or formic acid. The
6cooking liquor is washed from the pulp, and both cooking chemicals and water are
7recovered and recycled completely. Formic acid can also be used to enhance acetic
8acid pulping. The temperature and pressure can be lower when formic acid is used in
9pulping compared to those used in alcohol or acetic acid pulping. Organic acid lignin
10is an optimal feedstock for many value-added products, due to its lower molecular
11weight and higher reactivity (Kubo et al., 1998; Cetin and Ozmen, 2002). Another
12advantage of organic acid pulping is the retention of silica on the pulp fiber that
13facilitates the efficient recovery of cooking chemicals (Seisto and Poppius, 1997). The
14Organosolv pulping processes based on organic acid cooking are the Milox, Acetosolv
15and Formacell processes.
16
17The Milox process is an Organosolv pulping process which uses peroxyformic acid or
18peroxyacetic acid as the cooking chemical (Leponiemi, 2008). Peroxyformic or
19peroxyacetic acid are simple to prepare by equilibrium reaction between hydrogen
20peroxide and formic or acetic acids. These are highly selective chemicals that do not
21react with cellulose or other wood polysaccharides in the same way as formic acid.
22The hydrogen peroxide consumption is reduced by performing the process in two or
23three stages. The two-stage formic acid/peroxyformic acid process can be used to
24produce high viscosity (> 900 dm3/kg SCAN) and fully bleached (90 % ISO) pulp
25with a reasonable yield (40-48 %). The pulping stages are carried out at atmospheric

14

1pressure and at temperatures below 100 C. The resulting pulps have kappa numbers
2between 5 and 35. (Muurinen, 2000).
3
4The hydrogen peroxide charge needed can be reduced by using a three-stage cooking
5method. In the first stage, the temperature increases from 60C to 80C. The
6peroxyformic acid that forms is allowed to react with the cellulosic material for 0.5-1
7hours. The temperature is raised to the boiling point of the formic acid (ca. 105C)
8and cooking proceeds for 2-3 hours. The softened chips are then blown into another
9reactor, and the pulp is washed with pure formic acid. The washed pulp is then
10reheated with peroxyformic acid at 60C at about 10% consistency. Peroxide is
11applied to the liquor at 1%-2% of the original dry weight of the chips. After cooking,
12the pulp is washed with strong formic acid, pressed to 30%-40% consistency, and
13washed under pressure with hot water at 120C. This removes the chemically bonded
14formic acid. After washing and screening, the pulp is ready for bleaching.
15
16Unlike with wood species, the two-stage Milox pulping of agricultural plants is more
17effective than three-stage cooking. The two-stage process uses cooking with formic
18acid alone, followed by treatment with formic acid and hydrogen peroxide (Sundquist,
192000). When the Milox method is used to delignify agricultural plants, the resulting
20pulp contains all the silicon present in the plant. This enables the use of a similar
21chemical recycling system as in a corresponding wood pulping process. The silica is
22dissolved during the alkaline peroxide bleaching. (Muurinen, 2000). The two stage
23peroxyacetic acid process gives higher delignification than three-stage process and

15

1vice-versa with peroxyformic acid. The Milox process is a sulphur free process and
2bleaching can be achieved totally without chlorine chemicals (Sundquist, 2000).
3
4Acetic acid was one of the first organic acids used for the delignification of
5lignocellulosic raw material to produce pulp for paper. Processes based on the use of
6acetic acid as an organic solvent have been applied with success to hard and
7softwoods, and even to non-wood materials (Pan and Sano, 2005). It can be used as a
8pulping solvent in uncatalyzed systems (Acetocell method) or in catalyzed systems
9(the Acetosolv method) (Abad et al., 2003; Kin, 1990; Ligero et al., 2005; Pan et al.,
101999; Paraj et al., 1993; Vzquez et al., 1995; Young and Davis, 1986). The
11Acetosolv process is a hydrochloric acid catalysed (0.1%-0.2%) acetic acid process.

12The cooking temperature is 110 C and the process can be conducted at atmospheric
13pressure, or above (Nimz, 1989).
14
15Acetic acid used in pulping can be easily recovered by a stilling operation and reused
16in the process. Acetic acid lignin is an optimal feedstock for many value-added lignin
17products due to its lower molecular weight and higher reactivity. The sugars from
18hemicellulose are readily convertible to chemicals and fuels. It has already been
19reported by a number of researchers that the acetic acid pulping properties of woods
20are comparable to conventional chemical processes. They also have some advantages
21in comparison to other Organosolv processes (Groote et al., 1993; Sahin and Young,
222008).
23The Formacell process was developed from the Acetosolv process. It is an Organosolv
24pulping approach in which a mixture of formic and acetic acid is used as the cooking

16

1chemical (Leponiemi, 2008). Nimz and Schone (1993) have invented a process where
2lignocellulosic material is delignified under pressure with a mixture of acetic acid (50395 w-%), formic acid (< 40 w-%) and water (< 50 w-%). The pulping temperature is
4between 130

C and 190

C. Pulps with very low residual lignin contents are

5produced and they can be bleached to full brightness using ozone and peroxyacetic
6acid. Azeotropic distillation with butyl acetate is used to separate water from the
7acids. Low pulping temperatures and high acetic acid concentrations should be used in
8the Formacell process in order to preserve hemicelluloses for paper grade pulps. The
9use of higher temperatures and water concentrations in the pulping liquor results in
10dissolving pulps with hemicellulose contents below 3 % (Saake et al. 1995).
11Formacell pulps produced from annual plants have better strength properties than
12corresponding soda pulps (Sundquist, 2000).
13Factors of Delignification
14Important parameters controlling the delignification of the Organosolv pulping
15processes are the types of raw materials, the solvent properties, the chemical
16properties of catalysts and pulping conditions. The chemical composition of non17wood materials varies, depending on the non-wood species. Non-wood materials
18generally have higher silicon, nutrient and hemicellulose contents than wood (Hurter,
191988). By pre-treatment of the raw materials, part of the leaves and non-fibrous
20materials may be removed. This has a positive influence on the ash content and the
21pulp and paper properties; the chemical composition of the fibers, however, still
22remains different from paper processed from woods.
23The solvent properties have effects on the delignification and pulp properties of non24wood fibers. In Organosolv pulping, alcohols promote solvolysis reactions

17

1(McDonough, 1993; Sarkanen, 1990; Schroeter, 1991) but they also reduce the
2viscosity of the pulping liquor. This makes possible a better penetration and the
3diffusion of chemicals into fibrous materials (Balogh et al., 1992; Bendzala et al.,
41995). Ethanol and methanol are normally used as the pulping solvents. Both alcohols
5show similar selectivity when pulp total yield is considered, but higher screened yield
6values can be obtained in ethanol pulping. Methanol shows better lignin dissolution
7on average. However, ethanol pulping produces pulps with less lignin at high8intensity cooking conditions, where Kappa numbers lower than 10 can be obtained.
9The extent of delignification increases as the ethanol concentration is decreased (Oliet
10et al., 2002). The selectivity towards lignin dissolution is similar for ethanol and
11methanol.
12
13The most important differences are those observed for pulp viscosity. Although
14ethanol pulps have a higher viscosity on average, the best results are obtained from
15methanol pulping. Thus, viscosity values well over 1000 ml/g are obtained for pulps
16with Kappa numbers between 20 and 30 in the methanol system. These pulps, which
17are obtained under mild cooking conditions, are of special interest since they can be
18bleached and are obtained at a good screened yield. Ethanol provides lower viscosity
19pulp but at a slightly higher screened yield. In both cases, acceptable pulp Kappa
20numbers can be reached.
21
22The interest in ethanol and methanol pulping is not only justified in terms of cost. The
23acceptable quality of the pulp produced and the ease of recovery of the solvent by
24rectification also make the use of ethanol and methanol attractive. Furthermore, some

18

1valuable by-products, such as lignin and carbohydrates, can be obtained during

2solvent recovery. The ethanol solvent has mainly been used in autocatalyzed pulping,
3the ALCELL process, and antraquinone catalyzed pulping (Pye and Lora, 1991; Aziz
4and Sarkanen, 1989). The focus of methanol use has been alkaline pulping
5(Stockburger, 1993). However, it has been shown that pulps with low lignin content
6and acceptable viscosity can be obtained in an acidic medium by methanol
7autocatalyzed pulping (Gilarranz et al., 1999). Methanol has some interesting
8features, such as easy recovery by distillation, and has a lower material cost than
9ethanol. However, the use of methanol may be hazardous since methanol is a highly
10flammable and toxic chemical (Oliet et al., 2002).
11
12Aranovsky and Gortner (1936) found that primary alcohols were more selective
13delignifying agents than secondary or tertiary alcohols. The monovalent and
14polyvalent alcohols had higher pulping efficiencies in the presence of water. The use
15of methanol resulted in less hemicellulose loss than with -butanol. The higher
16pulping efficiency (better fiber separation) was associated with increased
17hemicellulose losses in the aqueous alcohol mixtures.
18
19When using organic acid solvents, the typical organic acid used as the pulping
20solvents are acetic and formic acid. Formic acid can also be used to enhance acetic
21acid pulping. Temperature and pressure can be lower when formic acid is used in
22pulping compared to that used in alcohol or acetic acid pulping (Rousu et al., 2002).
23The major influence was the acidity or acid concentration. Increasing acetic acid
24concentration reduced yield and lignin content. The solvent concentration had effects

19

1on the various mechanical properties (breaking length, burst, tear index and folding
2endurance) of paper sheets obtained from each pulping process. The extent of
3delignification was found to be associated with the systems hydrogen ion content.
4
5Hydrogen ion concentration plays a very important role in solvent pulping. This is
6because lignin dissolution is expected to be preceded by the acid-catalyzed cleavage
7of -aryl and -aryl ether linkages in the lignin macromolecule, and becomes soluble
8in the pulping liquor (Goyal et al., 1992). Delignification in cooking in high-alcohol
9concentration can be improved by the addition of mineral acids. A lower alcohol
10concentration favored faster delignification by virtue of a higher hydrogen ion
11concentration. Acidity increase at lower alcohol concentrations and at lower liquor-to12raw material ratios, but this did not translate into enhanced delignification, probably
13because of some lignin redeposition. Acidity also increased with increasing cook time.
14There are clear signs for the recondensation and deposition of lignin that is common
15in the Organosolv processes. However, organic acids, especially formic acid, are
16highly corrosive and cause severe corrosion problem in the processing equipment
17(Leponiemi, 2008).
18
19Operating conditions that lead to the best pulp quality are important to the Organosolv
20pulping of non-wood fibers. The actual cooking condition required is a function of
21solvent concentration, cooking temperature, cooking time, type of non-wood being
22cooked and the type of organosolv pulping process. Table 2 shows a range of pulping
23conditions from the literature and the pulp properties of Organosolv pulping
24processes.

20

1Chemical catalysts is a critical factor in accelerating delignification in the Organosolv

2pulping processes. Paszner and Cho (1989) discovered that salts of alkaline earth
3metals, such as calcium and magnesium chlorides, are effective catalysts in
4Organosolv liquors with high methanol and ethanol contents. They have applied these
5catalysts to the Organosolv pulping of several softwood and hardwood species as well
6as bagasse. Bleachable-grade pulps with exceptionally high yields were obtained in
7each case. The reported bleached pulp yields are 54-57% for softwoods, 57-62% for
8hardwoods, and 55% for bagasse. The strength properties of these pulps were
9essentially equal to those of corresponding bleached Kraft processes.
10
11Orth and Orth (1977) recommended the use of aluminium chloride (AlCl 3 * 6 H2O) as
12the preferred catalyst in solvents of aqueous glycol or glycol ether. They further
13indicated that organic acids such as formic, acetic, propionic, oxalic, malic, citric or
14phthalic acids were suitable catalysts, as did Paszner and Chang (1983). The use of
15these organic acids has proved to be a great improvement over the use of mineral
16acids because they facilitate pulping. In the presence of an acid catalyst, many high17boiling solvents allow the pulping process to be performed at ambient pressure, thus
18eliminating the need for a pressurized reactor. A brief review of the pH effects on
19solvent pulping will help in understanding the effect of catalysts to control
20delignification and fiber quality. The solvent type and pH control are both important
21factors. A drop in pH during solvent cooking is considered to be responsible for a
22number of effects. These include the condensation of the solvolytically liberated
23lignin, the extensive hydrolytic dissolution of hemicelluloses, degradation of the
24cellulose, and formation of solvent insoluble condensation products in the cooking
25liquor (Aziz et al., 1988).

21

1
2The Organosolv pulping conditions have effects on the delignification of fibrous
3materials. Acidic Organosolv pulping is facilitated by the hydrolysis of ether linkages
4between lignin and carbohydrate. The dissolved lignin decreases with increasing
5cooking time when the fibrous materials are pulped with organic acids, indicating that
6lignin condensation occurs during cooking. Condensation during pulping occurs to a
7greater extent with formic acid than with acetic acid, and to a greater extent with
8acetic acid than with propionic acid. Propionic acid was also observed to delignify
9more effectively than either of the other two acids. Lignin precipitation occurs in the
10ethanol pulping process due to either the reduction of the ethanol concentration in the
11washing process or the drop in temperature which causes a decrease in lignin
12solubility, or both.
13
14The influence of cooking conditions, as mention previously, have effects on the
15properties of paper obtained from each Organosolv pulping process. Sahin and Young
16(2008) found that the pulping of jute in acetic acid results in strength losses at higher
17temperatures and prolonged cooking. The severe pulping conditions cause the
18depolymerization reactions of the carbohydrates. The extended delignification, with
19increasing temperature, strongly affected the strength properties of paper. Increasing
20temperature and extending cooking time usually brings about 1050% reduced tear
21strength.
22For alkali ethanol pulping of rice straw (Navaee-Ardeh, et al., 2004), the breaking
23length, burst index and folding endurance of paper sheets were more affected by
24ethanol concentration than temperature. This was after a cooking time of 150 minutes.

22

1At a high cooking temperature these dependent variables were much more sensitive to
2changes in time than in an ethanol concentration. Sabatier et al. (1989) found that the
3acid catalyzed ethanol pulping process is less selective than the alkaline process. Soda
4ethanol pulping can produce paper-grade pulps of good strength with a saving of 50%
5of the sodium hydroxide or more, compared with plain soda pulping. The pulps
6obtained by the alcohol soda (NaOH-EtOHH2O) method had a better quality and
7lower kappa number than those from ethanol solvent (EtOH-H 2O). Adding
8anthraquinone (AQ), as a catalyst to the pulping by aqueous alcohol soda gave higher
9yields, lower kappa number and better strength (Physico-mechanical) properties. (El10Skhawy et al., 1995).
11
12Conclusions
13The increasing demands for paper and environmental concerns have increased the
14need for non-wood pulp as a low-cost raw material for papermaking. This has also led
15to the developing of alternative pulping technologies that are environmentally benign.
16Annual plants and agricultural residues appear to be well suited for papermaking due
17to them being an abundant and renewable. However, many factors influence the
18suitability of raw materials for use in papermaking. These include: the ease of
19pulping; the yield of usable pulp; the cost of collection and transportation of the fiber
20source; the presence of contaminants; and the availability of the fiber supply.
21Additional factors include fiber morphology, such as its composition and strength, the
22fiber length and diameter.
23The Organosolv pulping processes are alternatives to conventional pulping processes,
24and have environmental advantages. Organosolv pulping features an organic solvent

23

1in the pulping liquor which limits the emission of volatile sulfur compounds into the
2atmosphere and gives efficient chlorine-free bleaching. These processes should be
3capable of pulping all lignocellulose species with equal efficiency. Another major
4advantage of the Organosolv process is the formation of useful by-products such as
5furfural, lignin and hemicelluloses.
6
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23
24
25

1
1
2
3

4
5Fig. 1 Consumption of non-wood pulp in paper production
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

35

36

1
2
3
4
5Table 1 Physical and chemical properties of some non-woods used for papermaking
Properties

Unit

Rice

Wheat

Bagasse

Reed

Bamboo

Jute

Hemp

Kenaf

Avg. fiber

mm

straw
1.41

straw
1.48

1.70

grass
1.5

1.36-

2.5

(bast)
20

(bast)
2.74

length
Avg.

13

20

20

4.03
8-30

18

22

20

175:1

110:1

85:1

75:1

135-

139:1

1000:1

135:1

28-36

29-35

32-44

45

175:1
26-43

61

55-65

31-39

diameter
L/D ratio
Alpha

cellulose
Lignin
%
12-16
16-21
19-24
22
21-31
11.5
2-4
Pentosan
%
23-28
26-32
27-32
20
15-26
24
4-7
HWS
%
7.3
12.27
4.4
5.4
4.8
3.7
20.5
ABS
%
0.56
4.01
1.7
6.4
2.3
2.4
2.6
SS
%
57.7
43.58
33.9
34.8
24.9
28.5
Ash
%
15-20
4-9
1.5-5
3
1.7-5
1.6
5-7
Silica
%
9-14
3-7
0.7-3
2
1.5-3
<1
<1
6HWS: hot water solubility, ABS: alcohol benzene solubility, SS: 1%sodium hydroxide solubility

15-18
21-23
5.0
2.1
28.4
2-5
-

37

1Table 2 Some Organosolv pulping conditions of non-wood fibers

Title
Unit
ASAM
ASAE
Acetic
(Bagasse)
(Wheat
Acid (Jute)
L:M ratio
Cooking temp.
Cooking Time
Organic solvent

C
min
%

%
Na2SO3 charge
%
NaOH charge
%
Anthraquinone(AQ)
%
Kappa No.
%
Screened Yield
Nm/g
Tensile index
kPa.m2/g
Burst index
mN.m2/g
Tear index
Reference

ALCELL

Autocatalyzed
EtOH

CIMV

CIMV

CIMV

(Kenaf)

(wheat straw)

(Bagasse)

(Rice straw)

15:1
107

10:1
107

12:1
107

120
60:20:20
(FA:AA:Water)
50.4
43
2.14
3.27
Kham et al.,
2005

180
30:55:15
(FA:AA:water)
28.2
49.4
3.21
4.23
Lam et al.,
2004

180
20:60:20
(FA:AA:water)
45.8
52.9
2.52
4.38
Delmas et al.,
2003

3-5:1
170-180

straw)
7:1
170

7:1
195

7-10:1
200

(Core Hemp)
12:1
195

60-150
20 (MtOH)

60
50 (EtOH)

60
90 (AA)

60
60 (EtOH)

120
60 (EtOH)

16-18
3-6
61-63
Shukry et
al., 2000

14
3.5
0.1
16.4
56.1
3.2-4
7.3
Usta et al.,
1999

42-56
30
31.4
76
60
47.7
24
87.4
1.1
4.4
4.6
8.0
9.9
3.1
Sahin and
Winner et
Zomers et al,
Young,
al., 1997
1995
2008
2L:M : liquor to raw material ratio, MtOH: Methanol, EtOH: Ethanol, FA: Formic acid, AA: Acetic acid

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1